JP4979244B2 - Metalworking oil composition - Google Patents

Description

  The present invention relates to a lubricating oil composition used for metal processing of various metals including aluminum, magnesium and copper, and alloys thereof. Examples of processing methods that can be applied include metal processing such as cold, warm and hot rolling, drawing, ironing, drawing, pressing, cutting and grinding.

In plastic processing of metal, the higher the severity, the easier the material will adhere, and material components will accumulate on the tool surface, and if this becomes significant, the workability will be impaired. Taking press molding as an example, there are cases where the surface of the tool is polished or a new tool is used for each processing, and processing is continuously performed with the same tool. In the latter case, material deposition as described above occurs on the surface of the tool, and the degree thereof affects the life of the tool.
In order to prevent such material deposition on the tool surface, it is necessary to prevent the material from adhering. For that purpose, extreme pressure agents such as sulfur and phosphorus, and oily agents such as esters and fatty acids are used. Addition is considered (for example, refer patent documents 1-3). However, many of the above extreme pressure agents cause odor when added to metalworking oil, and the working environment is worsened especially when the temperature of the lubricated part becomes high under severe processing conditions. In addition, there is a possibility of causing surface defects such as discoloration of the material after processing, stain, etc.Moreover, since there is a process for removing the oil agent after processing, carefully select the type of extreme pressure agent and oil agent, It is desirable that the amount used is as small as possible.
In addition, when the processing conditions are severe, heat generation at the lubrication site becomes remarkable, which not only promotes adhesion, but also increases the risk of ignition, which is a serious problem for production.
JP 2003-165994 A JP 2005-272818 A JP-A-8-253789

  In view of the circumstances as described above, an object of the present invention is to provide a metalworking oil composition that is excellent in anti-adhesion performance and cooling performance even in severe metalworking and has little adverse effect on the work environment. is there.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have used metalworking oil obtained by adding a specific phosphorus-containing compound to a base oil such as mineral oil, thereby enabling metalworking under severe conditions. The present inventors have found that the adhesion in the process can be prevented, the cooling performance is excellent, and the adverse effect on the working environment is small, and the present invention has been completed.

（式中、Ｒ’は炭素数１〜４０のアルキル基、Ｒ”は炭素数３のアルキル基を示す。） That is, the metalworking oil composition of the present invention is based on the total amount of phosphorus-containing compounds having at least one selected from the group consisting of mineral oils, fats and oils, and having a structure of formula (A) as a base oil. A metal working oil composition used for metal working of aluminum, magnesium and copper and their alloys, characterized by containing 0.1 to 35% by mass and further containing an ester and / or a monohydric alcohol as an oiliness agent .

(Wherein, R 'is an alkyl group having a carbon number of 1 to 40, R "represents an alkyl group having 3 carbon atoms.)

  The metalworking oil composition of the present invention is excellent in that it prevents adhesion of materials under severe processing conditions, has excellent cooling performance, has a low risk of ignition, and does not cause deterioration of the working environment such as odor. Has characteristics.

Hereinafter, the present invention will be described in detail.
The base oil used in the metalworking oil composition of the present invention may be any of mineral oil, fats and oils, or a mixture thereof.

  Examples of mineral oil that can be used in the present invention include, for example, a kerosene fraction obtained by distillation of a paraffinic or naphthenic crude oil; a normal paraffin obtained by an extraction operation from the kerosene fraction; and a paraffinic or naphthenic fraction. Appropriate one or more refining treatments such as solvent deburring, solvent extraction, hydrocracking, solvent dewaxing, catalytic dewaxing, hydrorefining, sulfuric acid washing, and clay treatment for lubricating oil fractions obtained by crude oil distillation The thing refine | purified in combination is mentioned.

  The aromatic content in the mineral oil is not particularly limited, but if the work environment is important, it is preferably 25% by volume or less, more preferably 15% by volume or less, still more preferably 10% by volume or less, and still more preferably 8% by volume. % Or less, more preferably 5% by volume or less, even more preferably 2% by volume or less, and most preferably 1% by volume or less. Here, the aromatic content means a value measured according to the fluorescent indicator adsorption method of JIS K 2536 “Petroleum products-hydrocarbon type test”.

  The naphthene content is not particularly limited but is preferably 10% by volume or more, more preferably 15% by volume or more, still more preferably 20% by volume or more, still more preferably 25% by volume or more, and most preferably 30% by volume. % Or more. By making the naphthene content 10% by volume or more, workability is improved. On the other hand, the naphthene content is preferably 90% by volume or less, more preferably 80% by volume or less, still more preferably 75% by volume or less, and most preferably 70% by volume or less. By making the naphthene content 90% by volume or less, volatilization of the oil agent at room temperature can be prevented.

  The paraffin content in the mineral oil is preferably 5% by volume or more, more preferably 10% by volume or more, and still more preferably 20% by volume or more. By setting the paraffin content to 5% by volume or more, the odor of the oil agent can be prevented. On the other hand, the paraffin content is preferably 90% by volume or less, more preferably 80% by volume or less, and still more preferably 70% by volume or less. By making the paraffin content 90% by volume or less, it is possible to improve the effect of preventing adhesion during processing.

  In the present invention, the naphthene content and the paraffin content are determined by the molecular ion intensity obtained by mass spectrometry by FI ionization (using a glass reservoir). The measurement method is specifically shown below.

(1) An adsorption tube for elution chromatography having a diameter of 18 mm and a length of 980 mm is packed with 120 g of silica gel (grade 923 manufactured by Fuji Devison Chemical Co., Ltd.) activated by drying at about 175 ° C. for 3 hours. .
(2) Inject 75 ml of n-pentane and pre-wet the silica gel.
(3) About 2 g of the sample is precisely weighed, diluted with an equal volume of n-pentane, and the obtained sample solution is injected.
(4) When the liquid level of the sample solution reaches the upper end of the silica gel, 140 ml of n-pentane is injected to separate the saturated hydrocarbon component, and the eluate is recovered from the lower end of the adsorption tube.
(5) Apply the eluate to a rotary evaporator to distill off the solvent to obtain a saturated hydrocarbon component.
(6) Type analysis of saturated hydrocarbon components with a mass spectrometer. As an ionization method in mass spectrometry, FI ionization method using a glass reservoir is used, and JMS-AX505H manufactured by JEOL Ltd. is used as a mass spectrometer.

The measurement conditions are shown below.
Acceleration voltage: 3.0 kV, cathode voltage: −5 to −6 kV, resolution: about 500, emitter: carbon, emitter current: 5 mA, measurement range: mass number 35 to 700, auxiliary oven temperature: 300 ° C., separator temperature: 300 ° C, main oven temperature: 350 ° C, sample injection volume: 1 μl

The resulting molecular ion by mass spectrometry after isotope correction, paraffins from the mass number _{(C n H 2n + 2)} and naphthenes _{(C n H 2n, C n} H 2n-2, C n H 2n-4 ...) Are classified and arranged, the fraction of each ionic strength is obtained, and the content of each type with respect to the entire saturated hydrocarbon component is determined. Next, based on the content of the saturated hydrocarbon component, the content of paraffin and naphthene for the entire sample is determined.

  Details of data processing by the FI method mass spectrometry type analysis method are described in “Nisseki Review”, Vol. 33, No. 4, pages 135-142, particularly “2.2.3 Data Processing”. .

  The initial boiling point of mineral oil is preferably 150 ° C. or higher, more preferably 155 ° C. or higher, and still more preferably 160 ° C. or higher. By setting the initial boiling point of mineral oil to 150 ° C. or higher, volatilization of the oil agent at room temperature can be sufficiently prevented. On the other hand, the end point of mineral oil is preferably 350 ° C. or lower, more preferably 340 ° C. or lower, and further preferably 330 ° C. or lower. Further, the temperature difference between the initial boiling point and the end point of the mineral oil is preferably 100 ° C. or less, more preferably 90 ° C. or less, still more preferably 80 ° C. or less. By setting the temperature difference to 100 ° C. or less, it is possible to prevent the oil agent from volatilizing at room temperature. Here, the initial boiling point and the end point mean values measured in accordance with JIS K 2254 “Petroleum product-distillation test method”.

  Examples of the fats and oils that can be used in the present invention include beef tallow, lard, soybean oil, rapeseed oil, rice bran oil, coconut oil, palm oil, palm kernel oil, hydrogenated products thereof, or a mixture of two or more of these. .

  Synthetic oils that can be used in the present invention include, for example, polyolefins (ethylene-propylene copolymers, polybutenes, 1-octene oligomers, 1-decene oligomers, and hydrides thereof), alkylbenzenes, alkylnaphthalenes, monoesters ( Butyl stearate, octyl laurate, etc.), diester (ditridecyl glutarate, di-2-ethylhexyl adipate, diisodecyl adipate, ditridecyl adipate, di-2-ethylhexyl sepacate, etc.), polyester (trimellitic acid ester, etc.), Polyol esters (trimethylolpropane caprylate, trimethylolpropane pelargonate, pentaerythritol-2-ethylhexanoate, pentaerythritol pelargonate, etc.), polyoxyal Glycol, polyphenyl ether, dialkyl diphenyl ether, phosphate ester (tricresyl phosphate, etc.), fluorine-containing compound (perfluoropolyether, fluorinated polyolefin and the like), and silicone oil.

As a phosphorus containing compound for metalworking oil compositions of this invention, what has a structure of Formula (A) is used.

Wherein (A), R 'is an alkyl group having a carbon number of 1-40.

  The alkyl group may be linear or branched. Specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert- Butyl group, linear or branched pentyl group, linear or branched hexyl group, linear or branched heptyl group, linear or branched octyl group, linear or branched nonyl group, linear or branched decyl group, linear or branched undecyl group Group, linear or branched dodecyl group, linear or branched tridecyl group, linear or branched tetradecyl group, linear or branched pentadecyl group, linear or branched hexadecyl group, linear or branched heptadecyl group, linear or branched octadecyl group , Linear or branched nonadecyl group, linear or branched icosyl group, linear or branched heicosyl group, linear or branched docosyl group, linear or branched tricosyl group, linear or branched Branched tetracosyl group, a linear or branched triacontyl group, and the like can be given a straight-chain or branched tetracontyl group.

In formula (A), R ″ is an alkyl group having 3 carbon atoms . The alkyl group may be linear or branched, and specific examples include n -propyl group and isopropyl group. it can.

  In the present invention, the content of the phosphorus-containing compound represented by the formula (A) is based on the total amount of the metal processing oil composition, and the upper limit is 35% by mass or less, preferably 10% by mass or less, more preferably 5% by mass or less, More preferably, it is 3 mass% or less, Most preferably, it is 1 mass% or less, and a lower limit is 0.1 mass% or more, Preferably it is 0.3 mass% or more, More preferably, it is 0.5 mass% or more. Addition of a phosphorus-containing compound exceeding 35% by mass may lower the solubility in the base oil or adversely affect the performance as a metal processing oil. Further, discoloration of the processed material, surface defects such as stains, etc. May cause this. Further, a phosphorus-containing compound of less than 0.1% by mass is not preferable because sufficient processability may not be obtained. Further, when only a phosphorus-containing compound other than that represented by the formula (A) is added, good results cannot be obtained.

The metalworking oil composition of the present invention may contain an oily agent. The oily agent used in the present invention includes those usually used as an oily agent for lubricating oils. However, it is preferable to use at least one oily agent selected from the following in order to further improve processability.
(1) Ester (2) Monohydric alcohol

  As the (1) ester, the constituent alcohol may be a monohydric alcohol or a polyhydric alcohol, and the carboxylic acid may be a monobasic acid or a polybasic acid.

  As the monohydric alcohol, one having 1 to 24 carbon atoms is usually used, and such an alcohol may be linear or branched. Specific examples of the alcohol having 1 to 24 carbon atoms include methanol, ethanol, linear or branched propanol, linear or branched butanol, linear or branched octanol, and linear Or branched nonanol, linear or branched decanol, linear or branched undecanol, linear or branched dodecanol, linear or branched tridecanol, linear or branched tetra Decanol, linear or branched pentadecanol, linear or branched hexadecanol, linear or branched heptadecanol, linear or branched octadecanol, linear Or branched nonadecanol, linear or branched eicosanol, linear or branched heneicosanol, linear or branched Of Torikosanoru, it includes straight chain or branched tetracosanol, and mixtures thereof.

  As the polyhydric alcohol, those having 2 to 10 valences, preferably 2 to 6 valences are usually used. Specific examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, polyethylene glycol (3 to 15 mer of ethylene glycol), propylene glycol, dipropylene glycol, and polypropylene glycol (3 to 15 mer of propylene glycol), 1,3-propanediol, 1,2-propanediol, 1,3-butanediol, 1,4-butanediol, 2-methyl-1,2-propanediol, 2-methyl-1,3-propanediol, Dihydric alcohols such as 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol, neopentyl glycol; glycerin, polyglycerin (a dioctamer of glycerin, For example, diglycerin, triglycerin, te Laglycerin, etc.), trimethylol alkanes (trimethylol ethane, trimethylol propane, trimethylol butane, etc.) and their 2- to 8-mer, pentaerythritol and their 2- to 4-mer, 1,2,4-butanetriol 1,3,5-pentanetriol, 1,2,6-hexanetriol, 1,2,3,4-butanetetrol, sorbitol, sorbitan, sorbitol glycerin condensate, adonitol, arabitol, xylitol, mannitol, etc. Examples thereof include hydric alcohols; sugars such as xylose, arabinose, ribose, rhamnose, glucose, fructose, galactose, mannose, sorbose, cellobiose, maltose, isomaltose, trehalose, sucrose, and mixtures thereof.

  Among these, ethylene glycol, diethylene glycol, polyethylene glycol (ethylene glycol 3-10 mer), propylene glycol, dipropylene glycol, polypropylene glycol (propylene glycol 3-10 mer), 1,3-propanediol, 2-methyl-1,2-propanediol, 2-methyl-1,3-propanediol, neopentyl glycol, glycerin, diglycerin, triglycerin, trimethylolalkane (trimethylolethane, trimethylolpropane, trimethylolbutane, etc. ) And their 2-4 tetramers, pentaerythritol, dipentaerythritol, 1,2,4-butanetriol, 1,3,5-pentanetriol, 1,2,6-hexanetriol, 1,2 3,4 butane tetrol, sorbitol, sorbitan, sorbitol glycerin condensate, adonitol, arabitol, xylitol, divalent to hexavalent polyhydric alcohols, and mixtures thereof, such as mannitol and the like are more preferable. More preferred are ethylene glycol, propylene glycol, neopentyl glycol, glycerin, trimethylol ethane, trimethylol propane, pentaerythritol, sorbitan, and mixtures thereof.

  The monobasic acid constituting the ester oily agent according to the present invention is usually a fatty acid having 6 to 24 carbon atoms, which may be linear or branched, and may be saturated or unsaturated. Specifically, for example, linear or branched hexanoic acid, linear or branched octanoic acid, linear or branched nonanoic acid, linear or branched decanoic acid, linear or Branched undecanoic acid, linear or branched dodecanoic acid, linear or branched tridecanoic acid, linear or branched tetradecanoic acid, linear or branched pentadecanoic acid, linear or Branched hexadecanoic acid, linear or branched octadecanoic acid, linear or branched hydroxyoctadecanoic acid, linear or branched nonadecanoic acid, linear or branched eicosanoic acid, linear Or a saturated fatty acid such as branched heneicosanoic acid, linear or branched docosanoic acid, linear or branched tricosanoic acid, linear or branched tetracosanoic acid; Branched hexenoic acid, linear or branched heptenoic acid, linear or branched octenoic acid, linear or branched nonenic acid, linear or branched decenoic acid, linear or Branched undecenoic acid, linear or branched dodecenoic acid, linear or branched tridecenoic acid, linear or branched tetradecenoic acid, linear or branched pentadecenoic acid, linear or Branched hexadecenoic acid, linear or branched octadecenoic acid, linear or branched hydroxyoctadecenoic acid, linear or branched nonadecenoic acid, linear or branched eicosenoic acid, linear Unsaturated fatty acids such as linear or branched hecoosenoic acid, linear or branched docosenoic acid, linear or branched tricosenoic acid, linear or branched tetracosenoic acid, and Mixtures of al and the like. Of these, saturated fatty acids having 8 to 20 carbon atoms, unsaturated fatty acids having 8 to 20 carbon atoms, and mixtures thereof are particularly preferable.

  Examples of the polybasic acid constituting the ester oil-based agent include dibasic acids having 2 to 16 carbon atoms and trimellitic acid. The dibasic acid having 2 to 16 carbon atoms may be linear or branched, and may be saturated or unsaturated. Specifically, for example, ethanedioic acid, propanedioic acid, linear or branched butanedioic acid, linear or branched pentanedioic acid, linear or branched hexanedioic acid, linear Or branched octanedioic acid, linear or branched nonanedioic acid, linear or branched decanedioic acid, linear or branched undecanedioic acid, linear or branched dodecanedioic acid Acid, linear or branched tridecanedioic acid, linear or branched tetradecanedioic acid, linear or branched heptadecanedioic acid, linear or branched hexadecanedioic acid; linear or Branched hexenedioic acid, linear or branched octenedioic acid, linear or branched nonenedioic acid, linear or branched decenedioic acid, linear or branched undecenedioic acid , Linear or branched dodecenedioic acid, straight Include and mixtures thereof; Jo or branched tridecenoic acid, straight-chain or branched tetradecene diacid, linear or branched heptadecenoic acid, straight-chain or branched hexadecene diacid.

In addition, as an ester oily agent,
(1a) Monohydric alcohol and monobasic acid ester (1b) Polyhydric alcohol and monobasic acid ester (1c) Monohydric alcohol and polybasic acid ester (1d) Polyhydric alcohol and polybasic acid ester (1e) ) Mixed ester of monohydric alcohol, mixture of polyhydric alcohol and polybasic acid (1f) Mixed ester of polyhydric alcohol and mixture of monobasic acid, polybasic acid (1 g) Mixture of monohydric alcohol, polyhydric alcohol With a mixture of monobasic and polybasic acids
The ester by the combination of arbitrary alcohol and carboxylic acids, such as mixed ester, can be used, and is not specifically limited.

  In addition, when a polyhydric alcohol is used as an alcohol component, the complete ester in which all the hydroxyl groups in the polyhydric alcohol are esterified is shown. Further, when a polybasic acid is used as the carboxylic acid component, it may be a complete ester in which all the carboxyl groups in the polybasic acid are esterified, and a part of the carboxyl group is not esterified and remains as a carboxyl group. It may be a partial ester.

  As the ester used in the present invention, any of the above-mentioned esters can be used. Among these, (1a) an ester of a monohydric alcohol and a monobasic acid or (1c) a monohydric alcohol from the viewpoint of superior processability. And (1a) monohydric alcohol and monobasic acid ester, (1a) monohydric alcohol and monobasic ester, and (1c) monohydric alcohol and polybasic ester. It is most preferable to use in combination.

  (1a) The total carbon number of monohydric alcohol and monobasic acid ester used as an oily agent in the present invention is not particularly limited, but an ester having a total carbon number lower limit of 7 or more is preferable, and an ester of 9 or more Are more preferred, with 11 or more esters being most preferred. Further, an ester having an upper limit of the total carbon number of 26 or less is preferred, an ester of 24 or less is more preferred, and an ester of 22 or less is most preferred. Although there is no restriction | limiting in particular in carbon number of the said monohydric alcohol, C1-C10 is preferable, C1-C8 is more preferable, C1-C6 is still more preferable, C1-C4 is the most preferable. . Although there is no restriction | limiting in particular in carbon number of the said monobasic acid, C8-22 is preferable, C10-20 is more preferable, C12-18 is the most preferable. It is preferable to set the total carbon number, the carbon number of the alcohol, and the carbon number of the monobasic acid as described above. The upper limit value is likely to increase the occurrence of stain and corrosion, In consideration of the point that the fluidity is lost and the handling becomes difficult and the possibility that the solubility in the base oil is reduced and the precipitation is increased. This is because the working environment deteriorates due to odor.

The form of (1c) monohydric alcohol and polybasic acid ester used as an oily agent in the present invention is not particularly limited, but is preferably a diester represented by the following formula (1) or an ester of trimellitic acid. .
R ¹ —O—CO (CH ₂ ) _n CO—O—R ² (1)
[Wherein, R ¹ and R ² are the same or different from each other and represent a hydrocarbon group having 3 to 10 carbon atoms, and n represents 4 to 8. ]

R ¹ and R ² in the formula (1) are preferably hydrocarbon groups having 3 or more carbon atoms from the viewpoint that the effect of improving the lubrication performance may not be expected or the working environment is deteriorated by odor. . In addition, the possibility of increasing the occurrence of stains and corrosion increases, the possibility of losing fluidity and handling becomes difficult in winter, and the risk of precipitation due to reduced solubility in base oil increases. Therefore, in the formula (1), R ¹ and R ² are preferably hydrocarbon groups having 10 or less carbon atoms. In said Formula (1), n shows 4-8. From the point of increasing the possibility of increasing the occurrence of stains and corrosion, increasing the risk of losing fluidity in winter and becoming difficult to handle, increasing the possibility of precipitation due to lower solubility in base oil, etc. n is preferably 8 or less. Further, n is preferably 4 or more from the viewpoint that the effect of improving the lubrication performance may not be expected or the working environment is deteriorated by odor. Among these, n = 4 and 6 are particularly preferable from the viewpoint of availability of raw materials and price.

Examples of R ¹ and R ² of the diester include an alkyl group, an alkenyl group, an alkylcycloalkyl group, an alkylphenyl group, and a phenylalkyl group, and an alkyl group is particularly preferable. The alkyl group includes a linear alkyl group or a branched alkyl group, and a linear alkyl group and a branched alkyl group may be mixed, but a branched alkyl group is preferable.
Specific examples of R ¹ and R ² include linear or branched propyl group, linear or branched butyl group, linear or branched pentyl group, linear or branched hexyl group, linear or Examples thereof include a branched heptyl group, a linear or branched octyl group, a linear or branched nonyl group, and a linear or branched decyl group. The diester represented by the formula (1) can be obtained by any method. For example, a linear chain of 6 to 10 carbon atoms (adipic acid, pimelic acid, corkic acid, azelaic acid, sebacic acid in this order from 6 carbon atoms). Examples thereof include a method of esterifying a saturated dicarboxylic acid or a derivative thereof and an alcohol having 3 to 10 carbon atoms. The carbon number of the monohydric alcohol for esterifying trimellitic acid is not particularly limited, but there is a greater risk of increasing the occurrence of stains and corrosion, and there is a greater risk of loss of fluidity and difficulty in handling in winter. From the point that the solubility in oil decreases and the risk of precipitation increases, the number of carbon atoms is preferably 1 to 10, more preferably 1 to 8 carbon atoms, still more preferably 1 to 6 carbon atoms, and more preferably 1 to 1 carbon atoms. 4 is most preferred. The ester of trimellitic acid may be a partial ester (monoester or diester) or a complete ester (triester).

  Examples of the (2) monohydric alcohol used as the oily agent include the monohydric alcohol compounds listed as the alcohol constituting the (1) ester. Monohydric alcohols having 6 or more carbon atoms are preferable, alcohols having 8 or more carbon atoms are more preferable, alcohols having 10 or more carbon atoms are further preferable, and alcohols having 12 or more carbon atoms are more preferable. The alcohol is most preferred. It also increases the risk of increasing the occurrence of stains and corrosion, increases the risk of loss of fluidity during winter and increases the risk of handling, and increases the risk of precipitation due to decreased solubility in base oil Therefore, an alcohol having 20 or less carbon atoms is preferable, and an alcohol having 18 or less carbon atoms is more preferable.

  As the oily agent used in the metalworking oil composition of the present invention, as described above, only one kind selected from the above various oily agents may be used, or a mixture of two or more kinds may be used. From the viewpoint of lubricating performance, (1) esters and (2) monohydric alcohols are preferred, and (1) esters are more preferred.

  The total content of the oily agent is preferably 0.1 to 70% by mass based on the total amount of the composition. From the viewpoint of workability, the lower limit of the content is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and further preferably 0.5% by mass or more. In addition, the upper limit of the content is preferably 70% by mass or less, more preferably 60% by mass or less, from the viewpoint that if the content is too much, the occurrence of stains and corrosion may increase. Preferably it is 50% by weight or less, even more preferably 15% by weight or less, even more preferably 12% by weight or less, and most preferably 10% by weight or less.

  Moreover, the metalworking oil composition of this invention can further contain an extreme pressure agent, and preferable extreme pressure agents include phosphorus compounds other than the sulfur compounds described later and the compounds represented by formula (A). .

  The sulfur compound used in the present invention is not particularly limited as long as the properties of the metalworking oil composition are not impaired, but dihydrocarbyl polysulfide, sulfide ester, sulfide mineral oil, zinc dithiophosphate, zinc dithiocarbamate, dithiophosphorus A molybdenum acid compound and a molybdenum dithiocarbamate compound are preferably used.

The dihydrocarbyl polysulfide is a sulfur compound generally called polysulfide or sulfurized olefin, and specifically means a compound represented by the following general formula (2).
R ³ —S _h —R ⁴ (2)
[In Formula (2), R ³ and R ⁴ may be the same or different, and each has a linear or branched alkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or 6 carbon atoms. Represents an alkylaryl group of -20 or an arylalkyl group of 6-20 carbon atoms, h represents an integer of 2-6, preferably 2-5. ]

Specific examples of R ³ and R ⁴ in the general formula (2) include n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, straight chain or Branched pentyl group, linear or branched hexyl group, linear or branched heptyl group, linear or branched octyl group, linear or branched nonyl group, linear or branched decyl group, linear or branched undecyl group, linear or branched Dodecyl group, linear or branched tridecyl group, linear or branched tetradecyl group, linear or branched pentadecyl group, linear or branched hexadecyl group, linear or branched heptadecyl group, linear or branched octadecyl group, linear or branched nonadecyl A linear or branched alkyl group such as a linear or branched icosyl group; an aryl group such as a phenyl group or a naphthyl group; a tolyl group (including all structural isomers); Tilphenyl group (including all structural isomers), linear or branched propylphenyl group (including all structural isomers), linear or branched butylphenyl group (including all structural isomers), linear or branched Pentylphenyl group (including all structural isomers), linear or branched hexylphenyl group (including all structural isomers), linear or branched heptylphenyl group (including all structural isomers), linear or Branched octylphenyl group (including all structural isomers), linear or branched nonylphenyl group (including all structural isomers), linear or branched decylphenyl group (including all structural isomers), linear Or branched undecylphenyl group (including all structural isomers), linear or branched dodecylphenyl group (including all structural isomers), xylyl group (including all structural isomers), ethylmethyl Ruphenyl group (including all structural isomers), diethylphenyl group (including all structural isomers), di (linear or branched) propylphenyl group (including all structural isomers), di (linear or linear) Branched) butylphenyl group (including all structural isomers), methyl naphthyl group (including all structural isomers), ethyl naphthyl group (including all structural isomers), linear or branched propyl naphthyl group (all ), Linear or branched butyl naphthyl group (including all structural isomers), dimethyl naphthyl group (including all structural isomers), ethylmethyl naphthyl group (including all structural isomers) ), Diethyl naphthyl group (including all structural isomers), di (linear or branched) propyl naphthyl group (including all structural isomers), di (linear or branched) butyl naphthyl group (all structures) Alkylaryl group) and the like including sexual body; and the like can be given; benzyl group include phenyl ethyl (all isomers), an arylalkyl group such as a phenylpropyl group (including all isomers). Among these, R ³ and R ⁴ in the general formula (2), propylene, 1-butene or an alkyl group has been 3 to 18 carbon atoms derived from isobutylene, or an aryl group having a carbon number of 6-8, alkyl An aryl group or an arylalkyl group is preferable. Examples of these groups include isopropyl group, branched hexyl group derived from propylene dimer (including all branched isomers), and propylene trimer. Branched nonyl group derived (including all branched isomers), branched dodecyl group derived from propylene tetramer (including all branched isomers), branched derived from propylene pentamer Pentadecyl group (including all branched isomers), branched octadecyl group derived from propylene hexamer (including all branched isomers), sec A branched octyl group derived from a butyl group, a tert-butyl group, a 1-butene dimer (including all branched isomers), a branched octyl group derived from an isobutylene dimer (all branched forms) Isomers), branched dodecyl groups derived from 1-butene trimer (including all branched isomers), branched dodecyl groups derived from isobutylene trimer (all branched isomers) Branched hexadecyl group derived from 1-butene tetramer (including all branched isomers), branched hexadecyl group derived from isobutylene tetramer (including all branched isomers) Alkyl groups such as phenyl group, tolyl group (including all structural isomers), ethylphenyl group (including all structural isomers), xylyl group (including all structural isomers), etc. ; Examples thereof include arylalkyl groups such as benzyl group and phenylethyl group (including all isomers).
Furthermore, R ³ and R ⁴ in the above general formula (2) are each independently a branched alkyl group having 3 to 18 carbon atoms derived from ethylene or propylene from the viewpoint of improving the anti-adhesion performance. Are more preferable, and a branched alkyl group having 6 to 15 carbon atoms derived from ethylene or propylene is particularly preferable.

  Specific examples of the sulfurized ester include animal and vegetable fats and oils such as beef tallow, pork tallow, fish fat, rapeseed oil and soybean oil; unsaturated fatty acids (oleic acid, linoleic acid or fatty acids extracted from the above-mentioned animal and plant fats and the like) And an unsaturated fatty acid ester obtained by reacting various alcohols with each other; and those obtained by sulfiding a mixture thereof by any method.

  Sulfided mineral oil refers to one obtained by dissolving elemental sulfur in mineral oil. Here, the mineral oil used in the sulfide mineral oil according to the present invention is not particularly limited, and specifically, a lubricating oil fraction obtained by subjecting crude oil to atmospheric distillation and vacuum distillation is solvent desorbed and solvent extracted. , Hydrocracking, solvent dewaxing, catalytic dewaxing, hydrorefining, sulfuric acid washing, clay treatment, paraffinic mineral oil, naphthenic mineral oil and the like refined by appropriate combination. In addition, as the elemental sulfur, any form such as a lump, powder, molten liquid, etc. may be used, but when powdered or molten liquid elemental sulfur is used, it is efficiently dissolved in the base oil. Is preferable. In addition, molten liquid elemental sulfur has the advantage that the melting operation can be performed in a very short time because the liquids are mixed together, but it must be handled above the melting point of elemental sulfur, heating equipment, etc. It is not always easy to handle because it requires special equipment and is handled under a high temperature atmosphere. On the other hand, powdery simple sulfur is particularly preferable because it is inexpensive and easy to handle, and the time required for dissolution is sufficiently short. Moreover, although there is no restriction | limiting in particular in the sulfur content in the sulfide mineral oil concerning this invention, Preferably it is 0.05-1.0 mass% normally on the basis of the sulfide mineral oil whole quantity, More preferably, it is 0.1-0. 5% by mass.

A zinc dithiophosphate compound, a zinc dithiocarbamate compound, a molybdenum dithiophosphate compound and a molybdenum dithiocarbamate compound mean compounds represented by the following general formulas (3) to (6), respectively.

[In the formulas (3) to (6), R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ may be the same or different and each represents a hydrocarbon group having 1 or more carbon atoms, and X ¹ and X ² each represent an oxygen atom or a sulfur atom. ]

Here, R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ Specific examples of the hydrocarbon group represented by: methyl group, ethyl group, propyl group (including all branched isomers), butyl group (including all branched isomers), pentyl group (all Branched isomers), hexyl group (including all branched isomers), heptyl group (including all branched isomers), octyl group (including all branched isomers), nonyl group (all branched isomers) ), Decyl group (including all branched isomer pairs), undecyl group (including all branched isomer pairs), dodecyl group (including all branched isomer pairs), tridecyl group (including all branched isomer pairs) Including), tetradecyl group (all ), Pentadecyl group (including all branched isomer pairs), hexadecyl group (including all branched isomer pairs), heptadecyl group (including all branched isomer pairs), octadecyl group (all branched isomer pairs) Including isomeric pairs, nonadecyl group (including all branched isomer pairs), icosyl group (including all branched isomer pairs), heicosyl group (including all branched isomer pairs), docosyl group (all branched isomer pairs) ), Tricosyl group (including all branched isomer pairs), tetracosyl group (including all branched isomer pairs) and the like; cycloalkyl group such as cyclopentyl group, cyclohexyl group and cycloheptyl group; methylcyclopentyl group (Including all substituted isomers), ethylcyclopentyl group (including all substituted isomers), dimethylcyclopentyl (Including all substituted isomers), propylcyclopentyl group (including all branched isomers and substituted isomers), methylethylcyclopentyl group (including all substituted isomers), trimethylcyclopentyl group (all substituted isomers) ), Butylcyclopentyl group (including all branched and substituted isomers), methylpropylcyclopentyl group (including all branched and substituted isomers), and diethylcyclopentyl group (including all substituted isomers) ), Dimethylethylcyclopentyl group (including all substituted isomers), methylcyclohexyl group (including all substituted isomers), ethylcyclohexyl group (including all substituted isomers), dimethylcyclohexyl group (all substituted isomers) ), Propylcyclohexyl group (all branched isomers, Including methyl cyclohexyl group (including all substituted isomers), trimethyl cyclohexyl group (including all substituted isomers), butyl cyclohexyl group (including all branched isomers and substituted isomers) , Methylpropylcyclohexyl group (including all substituted isomers), diethylcyclohexyl group (including all substituted isomers), dimethylethylcyclohexyl group (including all substituted isomers), methylcycloheptyl group (Including all substituted isomers), ethylcycloheptyl group (including all substituted isomers), dimethylcycloheptyl group (including all substituted isomers), propylcycloheptyl group (all branched isomers, substituted) Isomers), methylethylcycloheptyl group (including all substituted isomers), Methylcycloheptyl group (including all substituted isomers), butylcycloheptyl group (including all branched isomers and substituted isomers), methylpropylcycloheptyl group (including all branched isomers and substituted isomers) Alkylcycloalkyl groups such as diethylcycloheptyl group (including all substituted isomers), dimethylethylcycloheptyl group (including all substituted isomers); aryl groups such as phenyl group and naphthyl group; tolyl group (all ), Xylyl group (including all substituted isomers), ethylphenyl group (including all substituted isomers), propylphenyl group (including all branched isomers, substituted isomers), Methylethylphenyl group (including all substituted isomers), trimethylphenyl group (including all substituted isomers), butylphenol Group (including all branched and substituted isomers), methylpropylphenyl group (including all branched and substituted isomers), diethylphenyl group (including all substituted isomers), dimethylethylphenyl Group (including all substituted isomers), pentylphenyl group (including all branched isomers and substituted isomers), hexylphenyl group (including all branched isomers and substituted isomers), heptylphenyl group (all Branched isomers, including substituted isomers), octylphenyl group (including all branched isomers and substituted isomers), nonylphenyl group (including all branched isomers and substituted isomers), decylphenyl group (including All branched isomers, including substituted isomers, undecylphenyl groups (including all branched isomers and substituted isomers), dodecylphenyl groups (all branched isomers) Isomers, including substituted isomers), tridecylphenyl group (including all branched isomers and substituted isomers), tetradecylphenyl group (including all branched isomers and substituted isomers), pentadecylphenyl group (Including all branched isomers and substituted isomers), hexadecylphenyl group (including all branched isomers and substituted isomers), heptadecylphenyl group (including all branched isomers and substituted isomers), Alkylaryl groups such as octadecylphenyl group (including all branched isomers and substituted isomers); benzyl group, phenethyl group, phenylpropyl group (including all branched isomers), phenylbutyl group (all branched isomers) Arylalkyl groups and the like.
In the present invention, among the above sulfur compounds, it is preferable to use at least one selected from the group consisting of dihydrocarbyl polysulfide and sulfurized ester because the effect of improving the anti-adhesion performance can be obtained at a higher level.

  Specific examples of the phosphorus-containing compound other than the compound represented by the formula (A) include, for example, phosphoric acid triester, acidic phosphoric acid ester, amine salt of acidic phosphoric acid ester, chlorinated phosphoric acid ester, phosphorous acid ester and Examples include phosphorothioate and metal salts of phosphorus compounds represented by the following general formula (7) or (8). Examples of these phosphorus compounds include esters of phosphoric acid, phosphorous acid or thiophosphoric acid and alkanols, polyether type alcohols, or derivatives thereof.

［式（７）中、Ｘ^３、Ｘ^４及びＸ^５は同一でも異なっていてもよく、それぞれ酸素原子又は硫黄原子を表し、Ｘ^３、Ｘ^４又はＸ^５の少なくとも２つは酸素原子であり、Ｒ^２１、Ｒ^２２、及びＲ^２３は同一でも異なっていてもよく、それぞれ水素原子又は炭素数１〜３０の炭化水素基を表す］

[In Formula (7), X ³ , X ⁴ and X ⁵ may be the same or different and each represents an oxygen atom or a sulfur atom, and at least two of X ³ , X ⁴ or X ⁵ are oxygen atoms. , R ²¹ , R ²² , and R ²³ may be the same or different and each represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms]

[In the formula (8), X ⁶ , X ⁷ , X ⁸ and X ⁹ may be the same or different and each represents an oxygen atom or a sulfur atom, and at least 3 of X ⁶ , X ⁷ , X ⁸ or X ⁹ One is an oxygen atom, and R ²⁴ , R ²⁵ and R ²⁶ may be the same or different and each represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. ]

  More specifically, phosphoric acid triesters include tributyl phosphate, tripentyl phosphate, trihexyl phosphate, triheptyl phosphate, trioctyl phosphate, trinonyl phosphate, tridecyl phosphate, triundecyl phosphate, tridodecyl phosphate, tritridecyl phosphate. Decyl phosphate, tritetradecyl phosphate, tripentadecyl phosphate, trihexadecyl phosphate, triheptadecyl phosphate, trioctadecyl phosphate, trioleyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, Xylenyl diphenyl phosphate and the like;

Examples of acidic phosphate esters include monobutyl acid phosphate, monopentyl acid phosphate, monohexyl acid phosphate, monoheptyl acid phosphate, monooctyl acid phosphate, monononyl acid phosphate, monodecyl acid phosphate, monoundecyl acid phosphate, monododecyl Acid phosphate, monotridecyl acid phosphate, monotetradecyl acid phosphate, monopentadecyl acid phosphate, monohexadecyl acid phosphate, monoheptadecyl acid phosphate, monooctadecyl acid phosphate, monooleyl acid phosphate, dibutyl acid phosphate, dipentyl acid , Dihexyl reed Dophosphate, diheptyl acid phosphate, dioctyl acid phosphate, dinonyl acid phosphate, didecyl acid phosphate, diundecyl acid phosphate, didodecyl acid phosphate, ditridecyl acid phosphate, ditetradecyl acid phosphate, dipentadecyl acid, dipentadecyl acid Hexadecyl acid phosphate, diheptadecyl acid phosphate, dioctadecyl acid phosphate, dioleyl acid phosphate, etc .;

Examples of the amine salt of acidic phosphate ester include methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, heptylamine, octylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, Salts with amines such as dipentylamine, dihexylamine, diheptylamine, dioctylamine, trimethylamine, triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, etc .;

Examples of the chlorinated phosphate ester include tris-dichloropropyl phosphate, tris-chloroethyl phosphate, tris-chlorophenyl phosphate, polyoxyalkylene bis [di (chloroalkyl)] phosphate, and the like;

As phosphites, dibutyl phosphite, dipentyl phosphite, dihexyl phosphite, diheptyl phosphite, dioctyl phosphite, dinonyl phosphite, didecyl phosphite, diundecyl phosphite, didodecyl phosphite, dioleyl Phosphite, diphenyl phosphite, dicresyl phosphite, tributyl phosphite, tripentyl phosphite, trihexyl phosphite, triheptyl phosphite, trioctyl phosphite, trinonyl phosphite, tridecyl phosphite, triundecyl phosphite Phyto, tridodecyl phosphite, trioleyl phosphite, triphenyl phosphite, tricresyl phosphite etc .;

The phosphorothioates include tributyl phosphorothioate, tripentyl phosphorothioate, trihexyl phosphorothionate, triheptyl phosphorothionate, trioctyl phosphorothionate, trinonyl phosphorothionate, tridecyl Phosphorothioate, triundecyl phosphorothionate, tridodecyl phosphorothioate, tritridecyl phosphorothioate, tritetradecyl phosphorothioate, tripentadecyl phosphorothionate, trihexadecyl phosphorothionate , Triheptadecyl phosphorothioate, trioctadecyl phosphorothioate, trioleyl phosphorothioate, triphenyl phosphorothioate, tri Resyl phosphorothioate, trixylenyl phosphorothioate, cresyl diphenyl phosphorothioate, xylenyl diphenyl phosphorothioate, tris (n-propylphenyl) phosphorothionate, tris (isopropylphenyl) phos Phosphorothionate, tris (n-butylphenyl) phosphothionate, tris (isobutylphenyl) phosphothionate, tris (s-butylphenyl) phosphothionate, tris (t-butylphenyl) phosphothionate, etc. Is mentioned.

Moreover, regarding the metal salt of the phosphorus compound represented by the general formula (7) or (8), as the hydrocarbon group having 1 to 30 carbon atoms represented by R ^{21 to} R ²⁶ in the formula, specifically, Includes an alkyl group, a cycloalkyl group, an alkenyl group, an alkylcycloalkyl group, an aryl group, an alkylaryl group, an arylalkyl group, and the like.

As the alkyl group, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, Examples include alkyl groups such as pentadecyl group, hexadecyl group, heptadecyl group, and octadecyl group (these alkyl groups may be linear or branched).
As said cycloalkyl group, C5-C7 cycloalkyl groups, such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, can be mentioned, for example. Examples of the alkylcycloalkyl group include a methylcyclopentyl group, a dimethylcyclopentyl group, a methylethylcyclopentyl group, a diethylcyclopentyl group, a methylcyclohexyl group, a dimethylcyclohexyl group, a methylethylcyclohexyl group, a diethylcyclohexyl group, a methylcycloheptyl group, Examples thereof include an alkylcycloalkyl group having 6 to 11 carbon atoms such as a dimethylcycloheptyl group, a methylethylcycloheptyl group, and a diethylcycloheptyl group (the substitution position of the alkyl group with the cycloalkyl group is also arbitrary).

Examples of the alkenyl group include butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, An alkenyl group such as an octadecenyl group (these alkenyl groups may be linear or branched, and the position of the double bond is also optional).
As said aryl group, aryl groups, such as a phenyl group and a naphthyl group, can be mentioned, for example. Examples of the alkylaryl group include tolyl group, xylyl group, ethylphenyl group, propylphenyl group, butylphenyl group, pentylphenyl group, hexylphenyl group, heptylphenyl group, octylphenyl group, nonylphenyl group, and decylphenyl. And alkylaryl groups having 7 to 18 carbon atoms such as an undecylphenyl group and dodecylphenyl group (the alkyl group may be linear or branched, and the substitution position on the aryl group is also arbitrary).
Examples of the arylalkyl group include arylalkyl groups having 7 to 12 carbon atoms such as benzyl group, phenylethyl group, phenylpropyl group, phenylbutyl group, phenylpentyl group, and phenylhexyl group (these alkyl groups are linear). Or may be branched).

The hydrocarbon group having 1 to 30 carbon atoms represented by R ^{21 to} R ²⁶ is preferably an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 24 carbon atoms, more preferably 3 to 3 carbon atoms. An alkyl group having 18 carbon atoms, more preferably an alkyl group having 4 to 12 carbon atoms.
R ²¹ , R ²² and R ²³ may be the same or different, and each represents a hydrogen atom or the above hydrocarbon group, and among R ²¹ , R ²² and R ²³ , 1 to 3 are the above hydrocarbon groups. It is preferable that 1 to 2 is the above hydrocarbon group, and more preferably 2 is the above hydrocarbon group.
R ²⁴ , R ²⁵ and R ²⁶ may be the same or different, and each represents a hydrogen atom or the above hydrocarbon group. Among R ²⁴ , R ²⁵ and R ²⁶ , 1 to 3 are the above hydrocarbons. It is preferably a group, 1 to 2 are more preferably the hydrocarbon group, and 2 are more preferably the hydrocarbon group.

In the general formula (7) phosphorus compounds represented by, at least two of X ³ to X ⁵ is required to be an oxygen atom, that all X ³ to X ⁵ is an oxygen atom preferable.
In the phosphorus compound represented by the general formula (8), at least three of X ^{6 to} X ⁹ are required to be oxygen atoms, but all of X ^{6 to} X ⁹ are oxygen atoms. It is preferable.

  Examples of the phosphorus compound represented by the general formula (7) include phosphorous acid and monothiophosphorous acid; phosphorous acid monoester having one hydrocarbon group having 1 to 30 carbon atoms and monothiophosphorous acid mono Ester; Phosphorous acid diester having two hydrocarbon groups having 1 to 30 carbon atoms, monothiophosphorous acid diester; Phosphorous acid triester having three hydrocarbon groups having 1 to 30 carbon atoms, monothiophosphorous acid Acid triesters; and mixtures thereof. Among these, phosphorous acid monoester and phosphorous acid diester are preferable, and phosphorous acid diester is more preferable.

  Examples of the phosphorus compound represented by the general formula (8) include phosphoric acid and monothiophosphoric acid; phosphoric acid monoester and monothiophosphoric acid monoester having one hydrocarbon group having 1 to 30 carbon atoms; And phosphoric acid diesters and monothiophosphoric acid diesters having two hydrocarbon groups having 1 to 30 carbon atoms; phosphoric acid triesters and monothiophosphoric acid triesters having three hydrocarbon groups having 1 to 30 carbon atoms; and mixtures thereof. It is done. Among these, phosphoric acid monoester and phosphoric acid diester are preferable, and phosphoric acid diester is more preferable.

  Examples of the metal salt of the phosphorus compound represented by the general formula (7) or (8) include a salt obtained by neutralizing part or all of the acidic hydrogen of the phosphorus compound with a metal base. Examples of the metal base to be used include metal oxides, metal hydroxides, metal carbonates, metal chlorides, and the like. Specific examples of the metal include alkali metals such as lithium, sodium, potassium, cesium, and calcium. And alkaline earth metals such as magnesium and barium, and heavy metals such as zinc, copper, iron, lead, nickel, silver, and manganese. Among these, alkaline earth metals such as calcium and magnesium and zinc are preferable.

  The metal salt of the phosphorus compound has a different structure depending on the valence of the metal and the number of OH groups or SH groups of the phosphorus compound. Therefore, the structure is not limited at all. For example, 1 mol of zinc oxide and phosphoric acid diester ( When 2 mol of 1 OH group is reacted, a compound having a structure represented by the following formula (9) is considered to be obtained as a main component, but it is also considered that polymerized molecules exist.

  In addition, for example, when 1 mol of zinc oxide and 1 mol of phosphoric acid monoester (two OH groups) are reacted, a compound having a structure represented by the following formula (10) is considered to be obtained as a main component. Polymerized molecules are also thought to exist.

  A mixture of two or more of these can also be used.

  In the present invention, among the above phosphorous compounds, phosphoric acid triesters, acidic phosphoric acid esters, amine salts of acidic phosphoric acid esters, and phosphorothioates are preferable because higher adhesion prevention performance improvement effects can be obtained.

  The metalworking oil composition of the present invention may contain only one of a sulfur compound or a phosphorus compound other than the compound represented by formula (A), and a phosphorus other than the sulfur compound and the compound represented by formula (A). It may contain both of the compounds. It is preferable that both the sulfur compound and the phosphorus compound other than the compound represented by the formula (A) are contained from the viewpoint that the effect of improving the anti-adhesion performance is further enhanced.

  Although the content of the extreme pressure agent is arbitrary, it is preferably 0.005% by mass or more and 0.01% by mass or more based on the total amount of the composition from the viewpoint of improving the anti-adhesion performance. More preferably, it is more preferably 0.05% by mass or more. From the viewpoint of preventing abnormal wear, the content of the extreme pressure agent is preferably 15% by mass or less, more preferably 10% by mass or less, and more preferably 7% by mass or less, based on the total amount of the composition. It is particularly preferred.

  Moreover, in the metalworking oil composition of this invention, the organic acid salt can be contained from the point from which the more outstanding adhesion prevention performance is acquired. As the organic acid salt, sulfonate, phenate, salicylate, and a mixture thereof are preferably used. Positive components of these organic acid salts include alkali metals such as sodium and potassium; alkaline earth metals such as magnesium, calcium and barium; ammonia, alkylamines having 1 to 3 carbon atoms (monomethylamine, dimethyl) Amine, trimethylamine, monoethylamine, diethylamine, triethylamine, monopropylamine, dipropylamine, tripropylamine, etc.), alkanolamines having 1 to 3 carbon atoms (monomethanolamine, dimethanolamine, trimethanolamine, Monoethanolamine, diethanolamine, triethanolamine, monopropanolamine, dipropanolamine, tripropanolamine, etc.), zinc and the like. Preferably metal or alkaline earth metal, calcium is particularly preferred. When the positive component of the organic acid salt is an alkali metal or alkaline earth metal, higher lubricity tends to be obtained.

  The total base number of the organic acid salt is preferably 50 to 500 mgKOH / g, more preferably 100 to 450 mgKOH / g. When the total base number of the organic acid salt is less than 50 mgKOH / g, the lubricity improving effect due to the addition of the organic acid salt tends to be insufficient. On the other hand, the organic acid salt having a total base number exceeding 500 mgKOH / g is Usually, since manufacture is very difficult and acquisition is difficult, it is unpreferable respectively. The total base number referred to here is JIS K 2501 “Petroleum products and lubricants—Test method for neutralization number”. The total base number (mgKOH / g) by the perchloric acid method measured according to the above.

  As the sulfonate, one produced by any method can be used. For example, alkali metal salts, alkaline earth metal salts, amine salts and mixtures of alkyl aromatic sulfonic acids obtained by sulfonating alkyl aromatic compounds having a molecular weight of 100 to 1500, preferably 200 to 700 are used. it can. As the alkyl aromatic sulfonic acid here, generally, a sulfonated alkyl aromatic compound in a lubricating oil fraction of mineral oil, a petroleum sulfonic acid such as so-called mahogany acid, which is produced as a by-product during white oil production, and a detergent A by-product from a raw material alkylbenzene production plant, a sulfonated alkylbenzene having a linear or branched alkyl group obtained by alkylating polyolefin to benzene, or an alkylnaphthalene such as dinonylnaphthalene Examples thereof include synthetic sulfonic acids such as those sulfonated. In addition, the above alkyl aromatic sulfonic acid and an alkali metal base (alkali metal oxide or hydroxide, etc.), an alkaline earth metal base (alkali earth metal oxide or hydroxide, etc.) or the above-mentioned So-called neutral (normal salt) sulfonates obtained by reacting with amines (ammonia, alkylamines, alkanolamines, etc.); neutral (normal salt) sulfonates, excess alkali metal bases, alkaline earth metal bases Or a so-called basic sulfonate obtained by heating an amine in the presence of water; reacting a neutral (normal salt) sulfonate with an alkali metal base, an alkaline earth metal base or an amine in the presence of carbon dioxide. So-called carbonate overbased (superbasic) sulfonates obtained by: neutral (normal salt) sulfonates with alkali metal bases, alkalis It reacts with bases or amines of similar metals and boric acid compounds such as boric acid or anhydrous boric acid, or reacts borate compounds such as boric acid or boric anhydride with carbonate overbased (superbasic) sulfonate And so-called borate overbased (superbasic) sulfonates produced by the above; and mixtures thereof.

  Further, as the phenate, specifically, in the presence or absence of elemental sulfur, an alkylphenol having 1 to 2 alkyl groups having 4 to 20 carbon atoms and an alkali metal base (alkali metal oxide or Hydroxides, etc.), alkaline earth metal bases (alkaline earth metal oxides, hydroxides, etc.) or the above-mentioned amines (ammonia, alkylamines, alkanolamines, etc.) and neutral Phenates; neutral phenates and excess alkali metal bases, alkaline earth metal bases or amines obtained by heating in the presence of water, so-called basic phenates; neutral phenates in the presence of carbon dioxide So-called carbonate overbased (superbasic) fluores obtained by reacting with metal bases, alkaline earth metal bases or amines. Nate; neutral phenate is reacted with alkali metal bases, alkaline earth metal bases or amines and boric acid compounds such as boric acid or boric anhydride, or carbonate overbased (superbasic) phenate and boron Examples include so-called borate overbased (superbasic) phenates produced by reacting boric acid compounds such as acid or boric anhydride; and mixtures thereof.

  Further, as the salicylate, specifically, an alkyl salicylic acid having 1 to 2 alkyl groups having 4 to 20 carbon atoms and an alkali metal base (alkali metal oxide) in the presence or absence of elemental sulfur. And hydroxides), alkaline earth metal bases (alkaline earth metal oxides and hydroxides, etc.) or amines mentioned above (ammonia, alkylamines, alkanolamines, etc.) So-called basic salicylate obtained by heating neutral salicylate and excess alkali metal base, alkaline earth metal base or amine in the presence of water; neutral salicylate in the presence of carbon dioxide gas So-called carbonate overbasing (super) obtained by reacting with alkali metal bases, alkaline earth metal bases or amines Basic) salicylates; neutral salicylates react with alkali metal bases, alkaline earth metal bases or amines and boric acid compounds such as boric acid or boric anhydride, or carbonate overbased (superbasic) Examples include so-called borate overbased (superbasic) salicylates produced by reacting metal salicylates with boric acid compounds such as boric acid or boric anhydride; and mixtures thereof.

  In the present invention, the organic acid salt may be used alone, or the organic acid salt and other additives may be used in combination. From the viewpoint of further improving the anti-adhesion performance, it is preferable to use an organic acid salt in combination with the above extreme pressure agent, and it is particularly preferable to use a combination of three types of sulfur compound, phosphorus compound and organic acid salt.

  The content of the organic acid salt is preferably 0.1 to 30% by mass, more preferably 0.5 to 25% by mass, and further preferably 1 to 20% by mass, based on the total amount of the composition. When the content of the organic acid salt is less than 0.1% by mass, the effect of improving the anti-adhesion performance due to the addition of the organic acid salt tends to be insufficient, and when the content exceeds 30% by mass, the metalworking oil composition There is a tendency that precipitates are likely to be produced due to a decrease in the stability of.

Moreover, in the metalworking oil composition of this invention, an alkanolamine or an amine can be contained from the point from which the more outstanding adhesion prevention performance is acquired.
As the alkanolamine, an alkanolamine having 1 to 12 carbon atoms, preferably 2 to 10 carbon atoms is used. Specific examples include, for example, monomethanolamine, dimethanolamine, trimethanolamine, monoethanolamine, diethanolamine, triethanolamine, mono (n-propanol) amine, di (n-propanol) amine, tri (n-propanol) Amines, monoisopropanolamine, diisopropanolamine, triisopropanolamine, monobutanolamine (including all isomers), dibutanolamine (including all isomers), tributanolamine (including all isomers), Monopentanolamine (including all isomers), dipentanolamine (including all isomers), tripentanolamine (including all isomers), monohexanolamine (including all isomers) , Dihexanolamine (all ), Monoheptanolamine (including all isomers), diheptanolamine (including all isomers), monooctanolamine (including all isomers), monononanolamine (including all isomers) Isomers included), monodecanolamine (including all isomers), monoundecanolamine (including all isomers), monododecanolamine (including all isomers), diethyl monoethanolamine , Diethyl monopropanolamine (including all isomers), diethyl monobutanolamine (including all isomers), diethyl monopentanolamine (including all isomers), dipropyl monoethanolamine (all isomers) Body), dipropyl monopropanolamine (including all isomers), dipropyl monobutanolamine (including all isomers) All isomers), dipropyl monopentanolamine (including all isomers), dibutyl monoethanolamine (including all isomers), dibutyl monopropanolamine (including all isomers), dibutyl Monobutanolamine (including all isomers), monoethyldiethanolamine, monoethyldipropanolamine (including all isomers), monoethyldibutanolamine (including all isomers), monoethyldipentanolamine (Including all isomers), monopropyldiethanolamine (including all isomers), monopropyldipropanolamine (including all isomers), monopropyldibutanolamine (including all isomers), mono Butyl diethanolamine (including all isomers), monobutyl dipropanol Min (including all isomers), monobutyldibutanolamine (including all isomers) and the like. Among these, preferred are monoethanolamine, diethanolamine, triethanolamine, mono (n-propanol) amine, di (n-propanol) amine, tri (n-propanol) amine, monoisopropanolamine, diisopropanolamine, Triisopropanolamine, monobutanolamine (including all isomers), dibutanolamine (including all isomers), diethylmonoethanolamine, diethylmonopropanolamine (including all isomers), diethylmonobutanolamine (Including all isomers), diethyl monopentanolamine (including all isomers), dipropyl monoethanolamine (including all isomers), dipropyl monopropanolamine (including all isomers) , Ziplo Rumonobutanolamine (including all isomers), dibutylmonoethanolamine (including all isomers), monoethyldiethanolamine, monoethyldipropanolamine (including all isomers), monoethyldibutanolamine (all ), Monopropyldiethanolamine (including all isomers), monopropyldipropanolamine (including all isomers), monobutyldiethanolamine (including all isomers), monobutyldipropanolamine Examples thereof include alkanolamines having 2 to 10 carbon atoms such as (including all isomers). Each of the above alkanolamines can be used alone, or a mixture of two or more alkanolamines having different structures can be used.

As the amine, an amine having 1 to 16 carbon atoms is used. The amine here includes an aliphatic amine, an aromatic substituted aliphatic amine, an alicyclic amine and an aromatic amine, and an aliphatic amine, an aromatic substituted aliphatic amine or an alicyclic amine is preferred. The aromatic-substituted aliphatic amine refers to an aromatic substituent bonded to the side chain of an alkyl group bonded to a nitrogen atom. Specific examples include, for example, aliphatic amines such as monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monopropylamine (including all isomers), dipropylamine (including all isomers), Tripropylamine (including all isomers), monobutylamine (including all isomers), dibutylamine (including all isomers), tributylamine (including all isomers), monopentylamine (all ), Dipentylamine (including all isomers), tripentylamine (including all isomers), monohexylamine (including all isomers), dihexylamine (including all isomers) ), Monoheptylamine (including all isomers), diheptylamine (all isomers) Including), monooctylamine (including all isomers), dioctylamine (including all isomers), monononylamine (including all isomers), monodecylamine (including all isomers), Monoundecyl (including all isomers), monododecylamine (including all isomers), dodecyldimethylamine (including all isomers), monotridecylamine (including all isomers), monotetradecyl C1-C16 aliphatic amines such as amine (including all isomers), monopentadecylamine (including all isomers), monohexadecylamine (including all isomers), and the like. Of these, aliphatic amines having 2 to 12 carbon atoms are preferred. Aromatic substituted aliphatic amines include monobenzylamine, (1-phenylethyl) amine, (2-phenylethyl) amine (monophenethylamine), dibenzylamine, bis (1-phenylethyl) amine, bis (2- Examples thereof include those having 7 to 16 carbon atoms such as (phenylethyl) amine (diphenethylamine), among which monobenzylamine and dibenzylamine are preferable. Examples of alicyclic amines include cycloalkylamines having 5 to 16 carbon atoms such as monocyclopentylamine, dicyclopentylamine, tricyclopentylamine, monocyclohexylamine, dicyclohexylamine, monocycloheptylamine, dicycloheptylamine; (methylcyclopentyl) ) Amine (including all substituted isomers), bis (methylcyclopentyl) amine (including all substituted isomers), (dimethylcyclopentyl) amine (including all substituted isomers), bis (dimethylcyclopentyl) amine ( Including all substituted isomers), (ethylcyclopentyl) amine (including all substituted isomers), bis (ethylcyclopentyl) amine (including all substituted isomers), (methylethylcyclopentyl) amine (all substituted isomers) Isomers), Sus (methylethylcyclopentyl) amine (including all substituted isomers), (Diethylcyclopentyl) amine (including all substituted isomers), (Methylcyclohexyl) amine (including all substituted isomers), Bis (methyl (Cyclohexyl) amine (including all substituted isomers), (dimethylcyclohexyl) amine (including all substituted isomers), bis (dimethylcyclohexyl) amine (including all substituted isomers), (ethylcyclohexyl) amine ( All substituted isomers), bis (ethylcyclohexyl) amine (including all substituted isomers), (methylethylcyclohexyl) amine (including all substituted isomers), (diethylcyclohexyl) amine (all substituted isomers) Isomers), (methylcycloheptyl) amine (all substituted isomers ), Bis (methylcycloheptyl) amine (including all substituted isomers), (dimethylcycloheptyl) amine (including all substituted isomers), (ethylcycloheptylamine (including all substituted isomers)) C6-C16 alkyl cycloalkylamines such as (methylethylcycloheptyl) amine (including all substituted isomers), (diethylcycloheptyl) amine (including all substituted isomers), and the like, Among them, a cycloalkylamine having 5 to 16 carbon atoms is preferable, among which an aliphatic amine having 2 to 12 carbon atoms, an aromatic substituted aliphatic amine having 7 to 16 carbon atoms, and a cycloalkylamine having 5 to 16 carbon atoms. And most preferred are aromatic substituted aliphatic amines having 7 to 16 carbon atoms and cycloalkylamines having 5 to 16 carbon atoms. is there. A single species of each of the above amines can be used, or a mixture of two or more amines having different structures can be used.
The content of the alkanolamine or amine is preferably 1 to 30% by mass, more preferably 2 to 25% by mass based on the total amount of the metal processing oil composition, and more preferable results can be obtained by using both in combination. .

The metalworking oil composition of the present invention can be suitably used as a water-insoluble metalworking oil substantially free of water, but can also be used as a water-soluble metalworking oil containing an effective amount of water. When used as a water-soluble metalworking oil, the content of water is in the range of 10 to 99% by mass, preferably 13 to 97% by mass, more preferably 15 to 95% by mass, based on the total amount of the composition. If the amount of water used is too small, the cooling property is insufficient, and if it is too much, the anti-adhesion property is insufficient. The water to be used can be tap water, industrial water, ion exchange water, distilled water or the like, regardless of whether the water is hard water or soft water. In the case of containing water, the composition of the present invention comprises a continuous layer of water in which an oil component is finely dispersed to form an emulsion, a solubilized state in which water is dissolved in the oil component, or strong. Any form of a suspension in which water and an oil are mixed by stirring can be used. In the case of the emulsion type, water is used as a continuous phase, and an emulsion in which oil components are finely dispersed is obtained. The average particle diameter of oil droplets dispersed in water is preferably 300 nm or less, particularly preferably 100 nm or less. This is because if the average particle size of the dispersed oil droplets is large, oil pits are easily generated and the surface gloss of the processed product is impaired, and a fine filter cannot be used for cleaning the metalworking fluid.
The metal processing oil composition of the present invention is preferably used as a water-insoluble metal processing oil because the effects of the present invention can be further exhibited.

The viscosity of the metalworking oil composition of the present invention is not particularly limited, but the kinematic viscosity at 40 ° C. is 0.05 to 500 mm ² / s, preferably 0.1 to 200 mm from the viewpoint of lubricity and surface quality. ² / s, more preferably 0.2 to 10 mm ² / s, and most preferably 0.3 to 8.0 mm ² / s.

  The metalworking oil composition of the present invention relates to a lubricating oil composition used for metalworking of various metals including aluminum, magnesium and copper, and alloys thereof. Examples of processing methods that can be applied include metal processing such as cold, warm and hot rolling, drawing, ironing, drawing, pressing, cutting and grinding.

  EXAMPLES Hereinafter, although the preferable Example of this invention is described further more concretely, this invention is not limited to these Examples.

(Examples 1-11 and Comparative Examples 1-10)
Using the components shown below, 16 types of metalworking oil compositions (8 types for Examples and 8 types for Comparative Examples) were prepared and subjected to rolling test 1, rolling test 2 and stain property test. Table 1 shows the composition of the metalworking oil composition of each example or comparative example.

(1) Base oil
Base Oil 1: kinematic viscosity at 40 ° C. 4.3 mm ² / s of the mineral base oil 2: mineral oil kinematic viscosity 7.6 mm ² / s at 40 ° C. (2) a phosphorus-containing compound a phosphorus compound 1: n-octyl phosphonic acid diisopropyl Esters (R = C ₈ )
Phosphorus compound 2: n-tetradecylphosphonic acid diisopropyl ester (R = C ₁₄ )
Phosphorus compound 3: n-octadecylphosphonic acid diisopropyl ester (R = C ₁₈ )
Phosphorus compound 4: n-tetracontylphosphonic acid diisopropyl ester (R = C ₂₄ )
(3) Oiliness agent Butyl stearate, lauryl alcohol (4) Other extreme pressure agents
Tricresyl phosphate (TCP), sulfurized ester, chlorinated paraffin (5) amines triethanolamine

In Examples 1 to 11 and Comparative Examples 1 to 10, the performance of each composition was evaluated by rolling test 1, rolling test 2 and stain test. The materials used for the test are the following five types.
Material 1: Pure aluminum (JIS A1050) Thickness 0.7mm, width 64mm
Material 2: Alloy aluminum (JIS A5052) Thickness 0.7mm, Width 64mm
Material 3: Pure copper (JIS C1100) Thickness 0.5mm, Width 60mm
Material 4: Brass (JIS C2600) Thickness 0.5mm, Width 60mm
Material 5: Phosphor bronze (JIS C5191) Thickness 0.5mm, Width 60mm

(Rolling test 1)
Using a work roll having a diameter of 50 mm and a roughness Ra = 0.8 μm, at the rolling speed of 80 m / min, test rolling is performed while gradually increasing the rolling reduction from 20%, and the maximum that can be rolled normally Obtain the reduction ratio.
(Rolling test 2)
Using a work roll having a diameter of 50 mm and a roughness Ra = 0.8 μm, test rolling is performed at a rolling speed of 300 m / min and a reduction rate of 40%, and the roll coating amount and material temperature (plate temperature) after the test are examined.
(Stainability test)
Put 2 ml of sample oil in a pure aluminum cup with a lid (diameter 6 cm, depth 1.2 cm), raise the temperature from room temperature to 350 ° C. over 1 hour and hold for 1 hour. Thereafter, the presence or absence of stain generation when cooled to room temperature is observed.

  The test results are shown in Table 1. When the phosphorus-containing compound (A) is not added (Comparative Examples 1, 3 to 10), the maximum rolling reduction is lower than that of the corresponding Examples, the roll coating amount is large, and the plate The temperature is also high. In addition, when the phosphorus-containing compound (A) is too much (Comparative Example 2), the maximum rolling reduction and the plate temperature are good, but stain is easily generated. In place of the phosphorus-containing compound (A), the maximum reduction can be achieved by adding a phosphorus compound other than (A) (TCP, Comparative Example 5), a sulfur compound (sulfurized ester, Comparative Example 6), and chlorinated paraffin (Comparative Example 7). The rate is not improved.

Claims (1)

One or more selected from the group consisting of mineral oil, fats and oils and synthetic oils are used as a base oil, and a phosphorus-containing compound having a structure of the formula (A) is contained in an amount of 0.1 to 35% by mass based on the total amount of the composition. A metalworking oil composition used for metalworking of aluminum, magnesium and copper and their alloys, characterized in that it contains an ester and / or a monohydric alcohol .

(Wherein, R 'is an alkyl group having a carbon number of 1 to 40, R "represents an alkyl group having 3 carbon atoms.)